Detergent-hydriodic acid compositions



United States Patent 3,367,877 DETERGENT-HYDRIUDIC ACll) COMPOSITIONSAbraham tCantor, Elkins Park, Pa, and William Schmidt,

Jamaica, N.Y., assigncrs to West Laboratories, Inc., Long island City,N.Y., a corporation of New York No Drawing. Filed Feb. 3, 1965, Ser. No.430,203 4 Claims. (Cl. 252-106) ABSTRACT OF THE DESCLGSURE Compositionsconsisting of hydriodic acid containing about 0.5 to 2.0 parts of waterper part by weight of H1, and a nonionic detergent, in which the weightpercentages of detergent and HI vary from a low acid composition havingabout 1% HI and 97.8% detergent to a compatible high acid compositionhaving not more than 40% HI and not less than detergent, said detergentbeing selected from the group consisting of nonionic surface activeagents and mixtures of nonionic surface active agents which have thecapacity to dissolve and complex with elemental iodine. Thesecompositions exhibit markedly reduced corrosiveness facilitating saferstorage, shipping and handling of H1. They provide useful concentratesfrom which to prepare germicidal detergent-iodine compositions by simpleroom temperature addition of elemental iodine.

compositions as starting components.

The value of hydriodic acid, HI, in germicidal detergentiodinecompositions has been disclosed in United States .Patent No. 3,028,299issued Apr. 3, 1962 jointly to Murray W. Winicov and William Schmidt,the present applicant. In said patent it is disclosed that formulationof detergent-iodine compositions to contain HI or alkali metal iodideproviding a source of (1) in excess of about 0.25 part per part ofiodine acts to stabilize the iodine and prevent the loss of availableiodine on standing that is normally experienced with detergent-iodinecomposition. The patent also points to the separate advantage of HI,when combined in an aqueous iodineiodide solution, in that it permitsrapid cold formulation of detergent-iodine compositions, whereas thedirect combining of detergent and elemental iodine ordinarily requiresextended heating.

Unfortunately, commercial aqueous HI (normally about 46% HI) and aqueousHI-iodine solutions are quite corrosive, presenting problems both instorage and shipment and in handling during formulating operations,requiring the use of special glass lined or other corrosion resistantequipment. Furthermore, the commercial grade (46%) aqueous HI isavailable from few sources in the United States, and is virtuallyunobtained in other countries, so that the problem of corrosiveness instorage and shipping constitutes a deterrent to more extensive use Of HIin detergent-iodine compositions.

It has now been discovered, in accordance with the present invention,that the advantages of HI in detergentiodine compositions can be fullyutilized, while substan- 3,367,877 Patented Feb. 6, 1968 tially reducingthe problem of corrosiveness, by combining aqueous hydriodic acid(suitably the commercial acid of about 46% concentration) withcompatible nonionic detergents which are known to be iodine carriers.The proportions of hydriodic acid to detergent can be varied to provide,per parts by weight, about 1 to 40 (and preferably 3 to 30) parts of HIand 97.8 to 10 (and pref erably 93.3 to 33) parts of detergent, thebalance to 100 parts being water introduced with the HI in thecommercial or technical grade hydriodic acid. With the normal variationin concentration of technical aqueous hydriodic acid, the proportion ofwater to HI in the composition Will fall within the range of about 0.5to 2.0 parts water per part by weight of HI.

The ability of nonionic detergent to reduce the corrosiveness of HI issurprising in view of the known practices of combining acid withdetergent to enhance metal cleaning and etching actions; and it isthought that the corrosion inhibiting may be due to a type of binding orcomplexing of HI with the nonionic detergent. This theory would appearto be supported by the fact that the new nonionic detergent-HIcompositions will readily dissolve elemental iodine by simple mixing atroom temperature, whereas iodine can be dissolved in the detergent aloneonly by extended mixing, preferably at substantially elevatedtemperature. Solutions of iodide, diluted with water, dissolve iodinewith difficulty, frequently taking as much as hours or days to dissolvethe same amount of iodine which would have dissolved readily in a moreconcentrated iodide solution. The same solutions of iodide, diluted withnonionic detergents as herein described dissolve iodine readily.

The new compositions are therefore uniquely adapted for'use ascommercial concentrates or starting components in the formulation ofconsumer products of the germicidal detergent-iodine type. Just as theseconsumer products vary widely in composition, depending on thegermicidal job to be done (the formulations differing, for example ingeneral purpose germicidal cleaners, dairy equipment cleaners,instrument cleaners for hospital use, germicidal rinses for commercialkitchen use, surgical scrub compositions, animal shampoos, and the like)so the formulation of the new detergent-HI concentrates can be widelyvaried to facilitate their use in the formulating of such consumerproducts. Suitably these concentrates can be utilized:

(a) By adding elemental iodine.

(b) By adding elemental iodine and then diluting with Water.

(c) By adding elemental iodine and then adding water plus an acid suchas phosphoric acid, hydroxyacetic acid or mixtures thereof.

(d) by following any of (a), (b), or (c), above plus the addition ofmore (of the same or different) detergent.

All of these formulating procedures can be carried out at roomtemperature and with conventional mixing equipment (except as the addedacid in procedure (c) may require special handling), thus for the firsttime making it commercially practical for the small formulator ofenvironmental sanitation products to formulate detergentiodine consumerproducts starting with elemental iodine as one of the components.

The new corn-positions provide a further economic advantage, sinceformulators can purchase iodine at the World price and add itthemselves, thereby avoiding the duties and handling charges on the mostexpensive constituent of ordinary concentrates. Since most detergentsand HI are currently available in the United States at a lower pricethan in other countries, the new compositions can also be shippedeconomically to other countries.

Any nonionic detergent selected from the group consisting of nonionicsurface active agents and mixtures of nonionic surface active agentswhich have the capacity to dissolve and complex with elemental iodinecan be blended with hydriodic acid to form one or more new concentratesand formulating components in accordance with the present invention.From the standpoint of cost, availability and general usefulness, thefollowing types of nonionic iodine carriers are of particular interest:

(a) Nonionic iodine carriers of the type disclosed in United StatesPatent No. 2,931,777 which are generally embraced by the formula:

wherein R represents the residue of a water insoluble organic compoundcontaining at least 6 carbon atoms, and have an active hydrogen and xrepresents an integer within the range of 6 to about 100; and

(b) Nonionic iodine carriers of the type disclosed in US. Patent No.2,759,869 and generally embraced by the formula:

where y equals at least 15 and (C H O) equals 20 to 90% of the totalweight of said compound.

Within the preferred range of proportions, i.e. in concentratescontaining up to about 30% HI most of the detergents embraced by theforegoing formulas form stable concentrates. As the proportion of HIapproaches or exceeds 30%, with the amount of water introduced with theHI (as technical aqueous hydriodic acid of about 46% concentration),care must be taken to provide an appropriate hydrophobic-hydrophilicbalance in the detergent. If a selected detergent will not form a stablesolution with an amount of aqueous hydriodic acid to provide 30 to 40%by weight of HI, then a similar detergent having a longer ethylene oxidechain, and increased hydrophilic properties, should be employed.

The following examples will provide a fuller understanding of thevarious adaptations and embodiments of the present invention, but it isto be understood that these examples are given by way of illustrationand not of limitation.

In the examples the iodine carriers identified by code or trade namehave the following chemical compositions:

Pluronic L-62=25 to 30 mols of polyoxypropylene condensed with 8.5 to10.2 mols of ethylene oxide.

Pluronic P65==25 to 30 mols of polyoxypropylene condensed with 33 to 40mols of ethylene oxide.

Igepal CO-710=nonyl phenol condensed with -11 mols of ethylene oxide.

Igepal CO-730=nonyl phenol condensed with about mols of ethylene oxide.

EXAMPLE I Two sets of detergent aqueous hydriodic acid concentrates wereprepared using in one set Pluronic L-62 (and Pluronic P-65 whereindicated) and in the other Igepal CO-710 as the detergent component;and a similar set of control concentrates was prepared containing onlywater and HI. The compositions and properties of these concentrates areshown in the following tabulations:

At 40% HI, 50% water and 10% detergent Pluronic L-62 does not form astable concentrate.

Concentrates 13 Legend 1 2 3 4 5 6 Percent Igepal CO-710 97. 8 93. 377.8 55.0 33.0 10.0 Percent III 1.0 3. 0 10.0 20. 0 30.0 40. 0 Percent HO i. 1.2 3.7 12.2 25. 0 37.0 50. 0 Viscosity at 50 C. (cps.) 220 370 705 Controls C Legend 1 2 3 4 5 6 Percent Water 99. 0 97.0 00.0 80.0 70.060.0 Percent HI 1. 0 3. 0 10. 0 20. 0 30. 0 40. 0 Viscosity at 50 C.(cps) 2 2 2 2 2 2 Concentrates A, B, and C were subjected to comparativetests using metal samples measuring approximately 1" x 2" x /e" andwarranted to meet A.S.T.M. D-1384 requirements (for antifreeze corrosiontesting).

In conducting the tests, the metal strips were scrubbed with a wirebrush in detergent solution, rinsed with water and then acetone, driedand weighed to the nearest milligram. The strips were then immersed in50 ml. portions of the test solutions for a period of 24 hours at 50 C.The strips were then removed, flushed with water, rinsed in acetone,dried and weighed. All tests were run in duplicate. The results in thefollowing tabulation shows the weight loss with concentrates A and B andcontrols C on five test metals:

WEIGHT LOSS (MG.)

Steel Alun Cast Iron Solder ri- Copper num Composition:

The test results tabulated above clearly indicate that in mostinstances, particularly at hydriodic acid concentrations of 1 to 30%,the compositions containing detergent (the A and B samples) caused muchless corrosion (weight loss) under the test conditions than the samplesC which contained no detergent.

In part, the corrosion inhibiting effect may be attributable to theviscosity increasing effect of the detergent, but separate tests haveshown that viscosity increase alone can account for only a portion ofthe corrosion reduction. By way of illustration, a solution was preparedcontaining 10% HI, 88.15% water, and thickened to a viscosity of 280cps. (at 50 C.) by the presence of 1.85% of carboxy polymethylene(Carbopol 941). In separate corrosion tests on aluminum according to theabove described procedure, this solution gave results of 113 mg. and 111mg. weight loss. These results are considerably greater than the weightloss values of 44 and 46 mg. for the comparable samples A-3 and B-3, asshown in the foregoing table.

In other comparative tests, a solution containing 20% HI, 78.1% waterand 1.9% carboxy polymethylene having a viscosity of 320 cps. (at 50 C.)showed a weight loss on aluminum of 260 and 210 mg. Here again theresults are significantly different from the weight loss of 5 112 and116 for the comparable samples A-4 and B-4 in the foregoing tabulation.

At the higher HI concentrations of 30% and 40%, the viscosities of thedetergent-HI solutions become so low that very little corrosionreduction can be attributed to a viscosity effect, and in the foregoingtabulations, the lower values for A-5 and B-5 compared with C-5, and forA6 and B6 compared with C-6, reflect primarily the detergent effect oncorrosion reduction.

In summary, the corrosion reduction effected by the detergent in the newcompositions is generally of the order of 50% or higher, and can be ashigh as 80 to 90% on some metals, particularly at the lower HIconcentrations.

The following additional examples show the preparation of typicaldetergent-HI concentrates suitable for commercial distribution and thenovel methods by which formulators may convert the same to differenttypes of consumer products.

EXAMPLE II 887 grams of Igepal CO-730 (paste), warmed to 35 C., wasplaced in a 1500 ml. beaker, equipped with a laboratory stirrer. 113grams'of (46% active) hydriodic acid was added, with stirring. Afteraddition was complete, mixing was continued for an additional 10minutes. The finished composition was analyzed and found to contain 5.0%hydriodic acid.

EXAMPLE III To 695 grams of Pluronic P-65 (paste), warmed to 40 C., wasadded 305 grams of (46% active) hydriodic acid, with stirring. Aftercompleting the addition, the batch was stirred for an additional lrninutes. The finished composition was analyzed and found to contain14.0% hydriodic acid.

EXAMPLE IV To 804 grams of Igepal CO-710 at 23 C., was added, withstirring, 196 grams of (46% active) hydriodic acid. After completingaddition, the batch was stirred for an additional 10 minutes. Thefinished composition was analyzed and found to contain 9.0% hydriodicacid.

EXAMPLE V To 565 grams of Pluronic L62 at 23 C., was added, withstirring, 435 grams of (46% active) hydriodic acid. After completing theaddition, the batch was stirred for an additional minutes. The finishedcomposition was analyzed and found to contain 20% hydriodic acid.

EXAMPLE VI To 870 grams of (46% active) hydriodic acid, at 23 C., wasadded, with stirring, 130 grams of Pluronic P-65 (paste-warmed to 40C.). After completing the addition, the batch was stirred for anadditional 5 minutes. The finished composition was analyzed and found tocontain 40% hydriodic acid.

Commercial hydriodic acid frequently contains traces of elemental iodinewhich is formed primarily as a result of the action of atmosphericoxygen on the highly acidic iodide solution. It is common practice toadd a very small amount of hypophosphorous acid (H PO to hydriodic acidsolutions to prevent this formation of free iodine. It has been foundthat hypophosphorous acid has a similar effect in preventing theformation of elemental iodine in the new detergent HI compositions, whenincluded in such compositions at the rate of about 0.05 to 0.5% andpreferably about 0.1 to 0.25% based on the weight of said compositions.It should be noted, however, that neither the small amount of iodinewhich may form in a detergent-HI composition, nor the small amount ofhypophosphorous acid which may be employed to inhibit its formation haveany appreciable effect on subsequent use of the detergent-HIcompositions in the formulation of detergent-iodine products.

The following examples are illustrative of detergent-HI compositionscontaining hypophosphorous acid:

EXAMPLE VII To 695 grams of Pluronic P-65 (paste), warmed to 40 C., wasadded 305 gm. of (40% active) hydriodic acid, with stirring. Aftercompleting the addition, the batch was stirred for an additional 10minutes during which time 2 grams of 50% aqueous HQPOZ was addedproviding 0.1% H PO in the product. The finished composition wasanalyzed and found to contain 12.2% HI.

EXAMPLE VIII To 695 grams of Pluronic P-65 (paste), warmed to 40 C., wasadded 305 gm. of (57% active) hydriodic acid, with stirring. Aftercompleting the addition, the batch was stirred for an additional 10minutes during which time 5 gm. of 50% aqueous H PO was added providing0.25% H PO in the product. The finished composition was analyzed andfound to contain 17.4% HI.

The following examples illustrate the novel formulating procedure ormethod which can be utilized in preparing detergentdodine concentratesand consumer products utilizing the new detergent-HI compositions asstarting components:

EXAMPLE TX 127 grams of the composition prepared. in Example II wasplaced in a 250 ml. beaker, equipped with a laboratory stirrer. 18.7grams of elemental iodine was added, with stirring, at an initialtemperature of 21 C. Mixing was continued for an additional 10 minutesat which time solution of the iodine was complete. The temperature ofthe batch was noted to increase from 21 C. to 28 C. after addition ofthe iodine.

After dissolving the iodine, the mixture was added to a 1500 ml. beakercontaining 854 grams of water and stirred until batch was homogenous.The finished product was found to contain 1.88% available iodine and2.54% total iodine (by Volhard).

EXAMPLE X 46.8 grams of the composition prepared in Example III wasplaced in a 250 ml. beaker equipped with a laboratory stirrer. 18.7grams of elemental iodine and 116.5 grams of Igepal CO-730 (paste-warmedto 30 C.) were added, with stirring. After solution of iodine wascomplete (approximately 10 minutes mixing time is required) the mixturewas added, with stirring, to a 1500 ml. beaker containing 818 grams of a19.5% phosphoric acid solution. After completing the addition, stirringwas continued for an additional 10 minutes.

The finished product was found to contain 1.89% available iodine, 2.55%total iodine (by Volhard) and 16.0% phosphoric acid.

EXAMPLE XI To 796 grams of the composition prepared in Example IV at 23C. was added 204 grams of elemental iodine, with stirring. Aftercompleting the addition, the batch was stirred for an additional 15minutes to complete solution of the iodine.

The finished product was found to contain 20.9% available iodine and27.8% total iodine (by Volhard).

EXAMPLE XII To 33.5 grams of the composition prepared in Example V at 23C. was added, with stirring, 18.7 grams of elemental iodine and 130grams of Igepal CO-730 (pastewarmed to 30 C.). After solution of theiodine was complete (approximately 10 minutes mixing time is required)the mixture was added, with stirring, to a 1500 ml. beaker containing817.8 grams of water. After completing the addition, stirring wascontinued for an additional 10 minutes. The finished product was foundto contain 7 1.88% available iodine and 2.54% total iodine (by Volhard).

EXAMPLE XIII To 17.0 grams of the composition prepared in Example VI at23 C. was added, with stirring, 18.7 grams of elemental iodine, 75 gramsof Igepal CO-71O and 75 grams of Igepal CO730 (paste-warmed to 30 C.).After completing the additions, the batch was stirred for an additional10 minutes to complete solution of the iodine.

The above mixture was then added, with stirring, to a 1500 ml. beakercontaining 814.3 grams of a 19.6% phosphoric acid solution. Aftercompleting the addition, stirring was continued for an additional 10minutes.

The finished product was found to contain 1.89% available iodine, 2.55%total iodine (by Volhard) and 16.0% phosphoric acid.

The products of Examples IX and XII are typical detergent-iodineconsumer products for general environmental sanitation purposes. Theproducts of Examples X and XIII are typical high acid detergent-iodineconsumer products suitable for use in the dairy industry and other areascharacterized by high concentrations of organic soil. The product ofExample XI can be used as an intermediate concentrate to be combinedwith added detergent and/ or acid and suitably diluted with water toform consumer products. While the products of Examples IX to XIII can beprepared by other formulating procedures, and no novelty is asserted inthese products, per se, it is considered that the new techniques usingthe novel detergent-HI compositions as starting components constitute animportant advancement of the detergentiodine art.

Various changes and modifications in the new compositions and methodsherein described may occur to those skilled in the art, and to theextent that such changes and modifications are embraced by the appendedclaims, it is to be understood that they constitute part of the presentinvention.

We claim:

1. A detergent-aqueous hydriodic acid composition consisting essentiallyof water, HI, and a nonionic detergent selected from the groupconsisting of nonionic surface active agents and mixtures of nonionicsurface active agents which have the capacity to dissolve and complexwith elemental iodine, water being present in the amount of about 0.5 to2.0 parts per part by weight of HI, the weight percentages of detergentand HI in said compositions varying from a low acid composition havingabout 1% HI and 97.8% detergent to a compatible high acid compositionhaving not more than HI and not less than 10% detergent, and all of theiodine present in said compositions being in the iodide form.

2. A detergent aqueous hydriodic acid composition as defined in claim 1,wherein the detergent and HI are present in the preferred range definedby a low acid composition having about 3% HI and 93.3% detergent and acompatible high acid composition having not more than 30% HI and notless than 33% detergent.

3. A detergent aqueous hydriodic acid composition as defined in claim 1,containing as a stabilizer for the HI an amount of H PO equivalent toabout 0.05 to 0.5% based on the weight of said composition.

4. A detergent aqueous hydriodic acid composition as defined in claim 1,containing as a stabilizer for the HI an amount of HgPO equivalent toabout 0.1 to 0.25% based on the weight of said composition.

References Cited UNITED STATES PATENTS 3,159,096 9/1964 Schmidt et al.252-l06 3,028,299 4/1962 Winicov et al. 167-l7 3,220,951 11/1965 Cantoret al. 252-106 LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN SCHNEIDER, Assistant Examiner.

